U.S. patent application number 10/456309 was filed with the patent office on 2004-12-09 for polyester process using a pipe reactor.
Invention is credited to Bonner, Richard Gill, DeBruin, Bruce Roger.
Application Number | 20040249111 10/456309 |
Document ID | / |
Family ID | 33490133 |
Filed Date | 2004-12-09 |
United States Patent
Application |
20040249111 |
Kind Code |
A1 |
DeBruin, Bruce Roger ; et
al. |
December 9, 2004 |
Polyester process using a pipe reactor
Abstract
There are disclosed polyester processes using a pipe reactor and
corresponding apparatuses. In particular, there are disclosed
processes and corresponding apparatuses including an esterification
pipe reactor operated in an upflow or downflow mode, especially in
a regime including stratified flow.
Inventors: |
DeBruin, Bruce Roger;
(Kingsport, TN) ; Bonner, Richard Gill;
(Kingsport, TN) |
Correspondence
Address: |
Charles R. Richard
Eastman Chemical Company
P.O. Box 511
Kingsport
TN
37662-5075
US
|
Family ID: |
33490133 |
Appl. No.: |
10/456309 |
Filed: |
June 6, 2003 |
Current U.S.
Class: |
528/271 ;
422/131; 528/272; 528/308; 528/308.1 |
Current CPC
Class: |
C08G 63/183 20130101;
C08G 63/785 20130101; B01J 19/2415 20130101 |
Class at
Publication: |
528/271 ;
528/272; 528/308; 528/308.1; 422/131 |
International
Class: |
C08G 063/00 |
Claims
What is claimed is:
1. A process for making a pre-polyester comprising: providing an
esterification pipe reactor comprising a pipe, the pipe having an
inlet and an outlet and constructed such that flow inside the pipe
from the inlet to the outlet follows a path that is not totally
vertical nor totally horizontal; and reacting one or more reactants
flowing in the pipe towards the outlet under esterification
reaction conditions to form the pre-polyester.
2. The process of claim 1 wherein the pipe is constructed such that
flow inside the pipe from the inlet to the outlet follows an
overall upward, but not totally vertical path.
3. The process of claim 2 wherein the pipe is substantially
empty.
4. The process of claim 2 wherein the pipe is constructed such that
flow inside the pipe from the inlet to the outlet follows an
overall upward, but not totally vertical path, with this path being
also generally non-downward, non-vertical.
5. The process of claim 4 wherein the pipe is substantially
empty.
6. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 2 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
7. The process of claim 6 wherein the step of reacting under
polycondensation reaction conditions is carried out in a
polycondensation pipe reactor.
8. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 3 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
9. The process of claim 8 wherein the step of reacting under
polycondensation reaction conditions is carried out in a
polycondensation pipe reactor.
10. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 4 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
11. The process of claim 10 wherein the step of reacting under
polycondensation reaction conditions is carried out in a
polycondensation pipe reactor.
12. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 5 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
13. The process of claim 12 wherein the step of reacting under
polycondensation reaction conditions is carried out in a
polycondensation pipe reactor.
14. The process of claim 2 further comprising removing vapor from
inside the pipe.
15. The process of claim 3 further comprising removing vapor from
inside the pipe.
16. The process of claim 4 further comprising removing vapor from
inside the pipe.
17. The process of claim 5 further comprising removing vapor from
inside the pipe.
18. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 14 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
19. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 17 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
20. The process of claim 2 wherein the pipe is serpentine.
21. The process of claim 3 wherein the pipe is serpentine.
22. The process of claim 4 wherein the pipe is serpentine.
23. The process of claim 5 wherein the pipe is serpentine.
24. The process of claim 2 further comprising adding a solubilizing
agent into the pipe.
25. The process of claim 3 further comprising adding a solubilizing
agent into the pipe.
26. The process of claim 4 further comprising adding a solubilizing
agent into the pipe.
27. The process of claim 5 further comprising adding a solubilizing
agent into the pipe.
28. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 24 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
29. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 27 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
30. The process of claim 24 wherein the solubilizing agent
comprises a polyester oligomer.
31. The process of claim 25 wherein the solubilizing agent
comprises a polyester oligomer.
32. The process of claim 26 wherein the solubilizing agent
comprises a polyester oligomer.
33. The process of claim 27 wherein the solubilizing agent
comprises a polyester oligomer.
34. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 30 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
35. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 33 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
36. The process of claim 2 wherein the reactants forming the
pre-polyester comprise a diacid, a diol, a diester, a hydroxy
ester, an acid ester, a hydroxy acid or combinations thereof.
37. The process of claim 3 wherein the reactants forming the
pre-polyester comprise a diacid, a diol, a diester, a hydroxy
ester, an acid ester, a hydroxy acid or combinations thereof.
38. The process of claim 4 wherein the reactants forming the
pre-polyester comprise a diacid, a diol, a diester, a hydroxy
ester, an acid ester, a hydroxy acid or combinations thereof.
39. The process of claim 5 wherein the reactants forming the
pre-polyester comprise a diacid, a diol, a diester, a hydroxy
ester, an acid ester, a hydroxy acid or combinations thereof.
40. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 36 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
41. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 39 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
42. The process of claim 2 wherein the reactants forming the
pre-polyester comprise TPA, DMT, CHDM, IPA, EG or combinations
thereof.
43. The process of claim 3 wherein the reactants forming the
pre-polyester comprise TPA, DMT, CHDM, IPA, EG or combinations
thereof.
44. The process of claim 4 wherein the reactants forming the
pre-polyester comprise TPA, DMT, CHDM, IPA, EG or combinations
thereof.
45. The process of claim 5 wherein the reactants forming the
pre-polyester comprise TPA, DMT, CHDM, IPA, EG or combinations
thereof.
46. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 42 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
47. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 45 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
48. The process of claim 2 further comprising adding a solubilizing
agent comprising a polyester oligomer into the pipe and wherein the
reactants forming the pre-polyester comprise TPA, DMT, CHDM, IPA,
EG or combinations thereof.
49. The process of claim 3 further comprising adding a solubilizing
agent comprising a polyester oligomer into the pipe and wherein the
reactants forming the pre-polyester comprise TPA, DMT, CHDM, IPA,
EG or combinations thereof.
50. The process of claim 4 further comprising adding a solubilizing
agent comprising a polyester oligomer into the pipe and wherein the
reactants forming the pre-polyester comprise TPA, DMT, CHDM, IPA,
EG or combinations thereof.
51. The process of claim 5 further comprising adding a solubilizing
agent comprising a polyester oligomer into the pipe and wherein the
reactants forming the pre-polyester comprise TPA, DMT, CHDM, IPA,
EG or combinations thereof.
52. The process of claim 14 further comprising adding a
solubilizing agent comprising a polyester oligomer into the pipe
and wherein the reactants forming the pre-polyester comprise TPA,
DMT, CHDM, IPA, EG or combinations thereof.
53. The process of claim 15 further comprising adding a
solubilizing agent comprising a polyester oligomer into the pipe
and wherein the reactants forming the pre-polyester comprise TPA,
DMT, CHDM, IPA, EG or combinations thereof.
54. The process of claim 16 further comprising adding a
solubilizing agent comprising a polyester oligomer into the pipe
and wherein the reactants forming the pre-polyester comprise TPA,
DMT, CHDM, IPA, EG or combinations thereof.
55. The process of claim 17 further comprising adding a
solubilizing agent comprising a polyester oligomer into the pipe
and wherein the reactants forming the pre-polyester comprise TPA,
DMT, CHDM, IPA, EG or combinations thereof.
56. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 48 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
57. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 51 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
58. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 52 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
59. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 55 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
60. The process of claim 6 wherein the polyester is PET or
PETG.
61. The process of claim 7 wherein the polyester is PET or
PETG.
62. The process of claim 8 wherein the polyester is PET or
PETG.
63. The process of claim 9 wherein the polyester is PET or
PETG.
64. The process of claim 10 wherein the polyester is PET or
PETG.
65. The process of claim 11 wherein the polyester is PET or
PETG.
66. The process of claim 12 wherein the polyester is PET or
PETG.
67. The process of claim 13 wherein the polyester is PET or
PETG.
68. The process of claim 2 wherein stratified flow appears in the
pipe.
69. The process of claim 3 wherein stratified flow appears in the
pipe.
70. The process of claim 4 wherein stratified flow appears in the
pipe.
71. The process of claim 5 wherein stratified flow appears in the
pipe.
72. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 68 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
73. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 69 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
74. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 70 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
75. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 71 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
76. The process of claim 2 wherein the liquid superficial velocity
is between 0.01 and 0.15 m/s and the vapor superficial velocity is
between 0.6 and 3.0 m/s across any full cross sectional area inside
the pipe perpendicular to the flow path in the pipe.
77. The process of claim 3 wherein the liquid superficial velocity
is between 0.01 and 0.15 m/s and the vapor superficial velocity is
between 0.6 and 3.0 m/s across any full cross sectional area inside
the pipe perpendicular to the flow path in the pipe.
78. The process of claim 4 wherein the liquid superficial velocity
is between 0.01 and 0.15 m/s and the vapor superficial velocity is
between 0.6 and 3.0 m/s across any full cross sectional area inside
the pipe perpendicular to the flow path in the pipe.
79. The process of claim 5 wherein the liquid superficial velocity
is between 0.01 and 0.15 m/s and the vapor superficial velocity is
between 0.6 and 3.0 m/s across any full cross sectional area inside
the pipe perpendicular to the flow path in the pipe.
80. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 76 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
81. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 77 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
82. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 78 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
83. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 79 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
84. The process of claim 2 wherein B.sub.x is less than 4.0 while
B.sub.y is less than 2.0 or B.sub.x is greater than or equal to 4.0
while (log.sub.10 B.sub.y) is less than or equal to
-0.677(log.sub.10 B.sub.x)+0.700 on average across any full cross
sectional area inside the pipe perpendicular to the flow path in
the pipe.
85. The process of claim 3 wherein B.sub.x is less than 4.0 while
B.sub.y is less than 2.0 or B.sub.x is greater than or equal to 4.0
while (log.sub.10 B.sub.y) is less than or equal to -0.677(log10
B.sub.x)+0.700 on average across any full cross sectional area
inside the pipe perpendicular to the flow path in the pipe.
86. The process of claim 4 wherein B.sub.x is less than 4.0 while
B.sub.y is less than 2.0 or B.sub.x is greater than or equal to 4.0
while (log.sub.10 B.sub.y) is less than or equal to -0.677(log 10
B.sub.x)+0.700 on average across any full cross sectional area
inside the pipe perpendicular to the flow path in the pipe.
87. The process of claim 5 wherein B.sub.x is less than 4.0 while
B.sub.y is less than 2.0 or B.sub.x is greater than or equal to 4.0
while (log.sub.10 B.sub.y) is less than or equal to
-0.677(log.sub.10 B.sub.x)+0.700 on average across any full cross
sectional area inside the pipe perpendicular to the flow path in
the pipe.
88. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 84 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
89. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 85 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
90. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 86 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
91. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 87 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
92. The process of claim 48 wherein stratified flow appears in the
pipe.
93. The process of claim 51 wherein stratified flow appears in the
pipe.
94. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 93 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
95. The process of claim 45 wherein the pipe is serpentine and
stratified flow appears in the pipe.
96. The process of claim 51 wherein the pipe is serpentine and
stratified flow appears in the pipe.
97. The process of claim 47 wherein the pipe is serpentine and
stratified flow appears in the pipe.
98. The process of claim 97 wherein the step of reacting under
polycondensation reaction conditions is carried out in a
polycondensation pipe reactor.
99. The process of claim 59 wherein the pipe is serpentine and
stratified flow appears in the pipe, the step of reacting under
polycondensation reaction conditions is carried out in a
polycondensation pipe reactor and the polyester is PET.
100. The process of claim 1 wherein the pipe is constructed such
that flow inside the pipe from the inlet to the outlet follows an
overall downward, but not totally vertical path.
101. The process of claim 100 wherein the pipe is substantially
empty.
102. The process of claim 100 wherein the pipe is constructed such
that flow inside the pipe from the inlet to the outlet follows an
overall downward, but not totally vertical path, with this path
being also generally non-upward, non-vertical.
103. The process of claim 102 wherein the pipe is substantially
empty.
104. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 100 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
105. The process of claim 104 wherein the step of reacting under
polycondensation reaction conditions is carried out in a
polycondensation pipe reactor.
106. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 101 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
107. The process of claim 106 wherein the step of reacting under
polycondensation reaction conditions is carried out in a
polycondensation pipe reactor.
108. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 102 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
109. The process of claim 108 wherein the step of reacting under
polycondensation reaction conditions is carried out in a
polycondensation pipe reactor.
110. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 103 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
111. The process of claim 110 wherein the step of reacting under
polycondensation reaction conditions is carried out in a
polycondensation pipe reactor.
112. The process of claim 100 further comprising removing vapor
from inside the pipe.
113. The process of claim 101 further comprising removing vapor
from inside the pipe.
114. The process of claim 102 further comprising removing vapor
from inside the pipe.
115. The process of claim 103 further comprising removing vapor
from inside the pipe.
116. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 112 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
117. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 115 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
118. The process of claim 100 further comprising removing vapor
from the pipe at a least one bend and wherein the pipe is
serpentine and has at least one weir at an effective distance from
a bend.
119. The process of claim 101 further comprising removing vapor
from the pipe at a least one bend and wherein the pipe is
serpentine and has at least one weir at an effective distance from
a bend.
120. The process of claim 102 further comprising removing vapor
from the pipe at a least one bend and wherein the pipe is
serpentine and has at least one weir at an effective distance from
a bend.
121. The process of claim 103 further comprising removing vapor
from the pipe at a least one bend and wherein the pipe is
serpentine and has at least one weir at an effective distance from
a bend.
122. The process of claim 100 further comprising adding a
solubilizing agent into the pipe.
123. The process of claim 101 further comprising adding a
solubilizing agent into the pipe.
124. The process of claim 102 further comprising adding a
solubilizing agent into the pipe.
125. The process of claim 103 further comprising adding a
solubilizing agent into the pipe.
126. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 122 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
127. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 125 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
128. The process of claim 122 wherein the solubilizing agent
comprises a polyester oligomer.
129. The process of claim 123 wherein the solubilizing agent
comprises a polyester oligomer.
130. The process of claim 124 wherein the solubilizing agent
comprises a polyester oligomer.
131. The process of claim 125 wherein the solubilizing agent
comprises a polyester oligomer.
132. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 128 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
133. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 131 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
134. The process of claim 100 wherein the reactants forming the
pre-polyester comprise a diacid, a diol, a diester, a hydroxy
ester, an acid ester, a hydroxy acid or combinations thereof.
135. The process of claim 101 wherein the reactants forming the
pre-polyester comprise a diacid, a diol, a diester, a hydroxy
ester, an acid ester, a hydroxy acid or combinations thereof.
136. The process of claim 102 wherein the reactants forming the
pre-polyester comprise a diacid, a diol, a diester, a hydroxy
ester, an acid ester, a hydroxy acid or combinations thereof.
137. The process of claim 103 wherein the reactants forming the
pre-polyester comprise a diacid, a diol, a diester, a hydroxy
ester, an acid ester, a hydroxy acid or combinations thereof.
138. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 134 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
139. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 137 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
140. The process of claim 100 wherein the reactants forming the
pre-polyester comprise TPA, DMT, CHDM, IPA, EG or combinations
thereof.
141. The process of claim 101 wherein the reactants forming the
pre-polyester comprise TPA, DMT, CHDM, IPA, EG or combinations
thereof.
142. The process of claim 102 wherein the reactants forming the
pre-polyester comprise TPA, DMT, CHDM, IPA, EG or combinations
thereof.
143. The process of claim 103 wherein the reactants forming the
pre-polyester comprise TPA, DMT, CHDM, IPA, EG or combinations
thereof.
144. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 140 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
145. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 143 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
146. The process of claim 100 further comprising adding a
solubilizing agent comprising a polyester oligomer into the pipe
and wherein the reactants forming the pre-polyester comprise TPA,
DMT, CHDM, IPA, EG or combinations thereof.
147. The process of claim 101 further comprising adding a
solubilizing agent comprising a polyester oligomer into the pipe
and wherein the reactants forming the pre-polyester comprise TPA,
DMT, CHDM, IPA, EG or combinations thereof.
148. The process of claim 102 further comprising adding a
solubilizing agent comprising a polyester oligomer into the pipe
and wherein the reactants forming the pre-polyester comprise TPA,
DMT, CHDM, IPA, EG or combinations thereof.
149. The process of claim 103 further comprising adding a
solubilizing agent comprising a polyester oligomer into the pipe
and wherein the reactants forming the pre-polyester comprise TPA,
DMT, CHDM, IPA, EG or combinations thereof.
150. The process of claim 112 further comprising adding a
solubilizing agent comprising a polyester oligomer into the pipe
and wherein the reactants forming the pre-polyester comprise TPA,
DMT, CHDM, IPA, EG or combinations thereof.
151. The process of claim 113 further comprising adding a
solubilizing agent comprising a polyester oligomer into the pipe
and wherein the reactants forming the pre-polyester comprise TPA,
DMT, CHDM, IPA, EG or combinations thereof.
152. The process of claim 114 further comprising adding a
solubilizing agent comprising a polyester oligomer into the pipe
and wherein the reactants forming the pre-polyester comprise TPA,
DMT, CHDM, IPA, EG or combinations thereof.
153. The process of claim 115 further comprising adding a
solubilizing agent comprising a polyester oligomer into the pipe
and wherein the reactants forming the pre-polyester comprise TPA,
DMT, CHDM, IPA, EG or combinations thereof.
154. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 146 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
155. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 149 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
156. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 150 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
157. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 153 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
158. The process of claim 104 wherein the polyester is PET or
PETG.
159. The process of claim 105 wherein the polyester is PET or
PETG.
160. The process of claim 106 wherein the polyester is PET or
PETG.
161. The process of claim 107 wherein the polyester is PET or
PETG.
162. The process of claim 108 wherein the polyester is PET or
PETG.
163. The process of claim 109 wherein the polyester is PET or
PETG.
164. The process of claim 110 wherein the polyester is PET or
PETG.
165. The process of claim 111 wherein the polyester is PET or
PETG.
166. The process of claim 100 wherein stratified flow appears in
the pipe.
167. The process of claim 101 wherein stratified flow appears in
the pipe.
168. The process of claim 102 wherein stratified flow appears in
the pipe.
169. The process of claim 103 wherein stratified flow appears in
the pipe.
170. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 166 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
171. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 167 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
172. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 168 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
173. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 169 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
174. The process of claim 100 wherein the liquid superficial
velocity is between 0.01 and 0.15 m/s and the vapor superficial
velocity is between 0.6 and 3.0 m/s across any full cross sectional
area inside the pipe perpendicular to the flow path in the
pipe.
175. The process of claim 101 wherein the liquid superficial
velocity is between 0.01 and 0.15 m/s and the vapor superficial
velocity is between 0.6 and 3.0 m/s across any full cross sectional
area inside the pipe perpendicular to the flow path in the
pipe.
176. The process of claim 102 wherein the liquid superficial
velocity is between 0.01 and 0.15 m/s and the vapor superficial
velocity is between 0.6 and 3.0 m/s across any full cross sectional
area inside the pipe perpendicular to the flow path in the
pipe.
177. The process of claim 103 wherein the liquid superficial
velocity is between 0.01 and 0.15 m/s and the vapor superficial
velocity is between 0.6 and 3.0 m/s across any full cross sectional
area inside the pipe perpendicular to the flow path in the
pipe.
178. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 174 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
179. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 175 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
180. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 176 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
181. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 177 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
182. The process of claim 100 wherein B.sub.x is less than 4.0
while B.sub.y is less than 2.0 or B.sub.x is greater than or equal
to 4.0 while (log.sub.10 B.sub.y) is less than or equal to
-0.677(log.sub.10 B.sub.x)+0.700 on average across any full cross
sectional area inside the pipe perpendicular to the flow path in
the pipe.
183. The process of claim 101 wherein B.sub.x is less than 4.0
while B.sub.y is less than 2.0 or B.sub.x is greater than or equal
to 4.0 while (log.sub.10 B.sub.y) is less than or equal to
-0.677(log.sub.10 B.sub.x)+0.700 on average across any full cross
sectional area inside the pipe perpendicular to the flow path in
the pipe.
184. The process of claim 102 wherein B.sub.x is less than 4.0
while B.sub.y is less than 2.0 or B.sub.x is greater than or equal
to 4.0 while (log.sub.10 B.sub.y) is less than or equal to
-0.677(log.sub.10 B.sub.x)+0.700 on average across any full cross
sectional area inside the pipe perpendicular to the flow path in
the pipe.
185. The process of claim 103 wherein B.sub.x is less than 4.0
while B.sub.y is less than 2.0 or B.sub.x is greater than or equal
to 4.0 while (log.sub.10 B.sub.y) is less than or equal to
-0.677(log.sub.10 B.sub.x)+0.700 on average across any full cross
sectional area inside the pipe perpendicular to the flow path in
the pipe.
186. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 182 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
187. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 183 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
188. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 184 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
189. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 185 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
190. The process of claim 146 wherein stratified flow appears in
the pipe.
191. The process of claim 149 wherein stratified flow appears in
the pipe.
192. A process for making a polyester oligomer, a polyester or both
comprising: performing the process according to claim 191 to make a
pre-polyester; and reacting the pre-polyester and optionally other
reactants, under polycondensation reaction conditions, to form the
polyester oligomer, the polyester or both.
193. The process of claim 143 wherein the pipe is serpentine and
stratified flow appears in the pipe.
194. The process of claim 149 wherein the pipe is serpentine and
stratified flow appears in the pipe.
195. The process of claim 145 wherein the pipe is serpentine and
stratified flow appears in the pipe.
196. The process of claim 195 wherein the step of reacting under
polycondensation reaction conditions is carried out in a
polycondensation pipe reactor.
197. The process of claim 157 wherein the pipe is serpentine and
stratified flow appears in the pipe, the step of reacting under
polycondensation reaction conditions is carried out in a
polycondensation pipe reactor and the polyester is PET.
198. An apparatus for making a pre-polyester comprising: an
esterification pipe reactor comprising a pipe, the pipe having an
inlet and an outlet and constructed such that flow inside the pipe
from the inlet to the outlet follows a path that is not totally
vertical nor totally horizontal, and wherein pre-polyester forming
reactants are passed towards the outlet.
199. The apparatus of claim 198 wherein the pipe is constructed
such that flow inside the pipe from the inlet to the outlet follows
an overall upward, but not totally vertical path.
200. The apparatus of claim 199 wherein the pipe is substantially
empty.
201. The apparatus of claim 199 wherein the pipe is constructed
such that flow inside the pipe from the inlet to the outlet follows
an overall upward, but not totally vertical path, with this path
being also generally non-downward, non-vertical.
202. The apparatus of claim 201 wherein the pipe is substantially
empty.
203. An apparatus for making a polyester oligomer, a polyester or
both comprising: the apparatus of claim 199 and a polycondensation
reactor connected to the outlet of the pipe.
204. The apparatus of claim 203 wherein the polycondensation
reactor is a polycondensation pipe reactor.
205. An apparatus for making a polyester oligomer, a polyester or
both comprising: the apparatus of claim 200 and a polycondensation
reactor connected to the outlet of the pipe.
206. The apparatus of claim 205 wherein the polycondensation
reactor is a polycondensation pipe reactor.
207. An apparatus for making a polyester oligomer, a polyester or
both comprising: the apparatus of claim 201 and a polycondensation
reactor connected to the outlet of the pipe.
208. The apparatus of claim 207 wherein the polycondensation
reactor is a polycondensation pipe reactor.
209. An apparatus for making a polyester oligomer, a polyester or
both comprising: the apparatus of claim 202 and a polycondensation
reactor connected to the outlet of the pipe.
210. The apparatus of claim 209 wherein the polycondensation
reactor is a polycondensation pipe reactor.
211. The apparatus of claim 201 further comprising means for
removing vapor from inside the pipe at at least one point along the
pipe.
212. The apparatus of claim 202 further comprising means for
removing vapor from inside the pipe at at least one point along the
pipe.
213. The apparatus of claim 199 wherein the pipe is serpentine.
214. The apparatus of claim 200 wherein the pipe is serpentine.
215. The apparatus of claim 201 wherein the pipe is serpentine.
216. The apparatus of claim 202 wherein the pipe is serpentine.
217. The apparatus of claim 201 further comprising a tank for
holding solubilizing agent connected to the pipe at a point other
than the outlet.
218. The apparatus of claim 201 further comprising a recycle line
connecting the pipe at a point nearer to the outlet than the inlet
with the pipe at a point nearer the inlet than the outlet.
219. The apparatus of claim 207 further comprising a flow line from
the polycondensation reactor to the pipe at a point other than the
outlet.
220. The apparatus of claim 198 wherein the pipe is constructed
such that flow inside the pipe from the inlet to the outlet follows
an overall downward, but not totally vertical path.
221. The apparatus of claim 220 wherein the pipe is substantially
empty.
222. The apparatus of claim 220 wherein the pipe is constructed
such that flow inside the pipe from the inlet to the outlet follows
an overall downward, but not totally vertical path, with this path
being also generally non-upward, non-vertical.
223. The apparatus of claim 222 wherein the pipe is substantially
empty.
224. An apparatus for making a polyester oligomer, a polyester or
both comprising: the apparatus of claim 220 and a polycondensation
reactor connected to the outlet of the pipe.
225. The apparatus of claim 224 wherein the polycondensation
reactor is a polycondensation pipe reactor.
226. An apparatus for making a polyester oligomer, a polyester or
both comprising: the apparatus of claim 221 and a polycondensation
reactor connected to the outlet of the pipe.
227. The apparatus of claim 226 wherein the polycondensation
reactor is a polycondensation pipe reactor.
228. An apparatus for making a polyester oligomer, a polyester or
both comprising: the apparatus of claim 222 and a polycondensation
reactor connected to the outlet of the pipe.
229. The apparatus of claim 228 wherein the polycondensation
reactor is a polycondensation pipe reactor.
230. An apparatus for making a polyester oligomer, a polyester or
both comprising: the apparatus of claim 223 and a polycondensation
reactor connected to the outlet of the pipe.
231. The apparatus of claim 230 wherein the polycondensation
reactor is a polycondensation pipe reactor.
232. The apparatus of claim 222 further comprising means for
removing vapor from inside the pipe at at least one point along the
pipe.
233. The apparatus of claim 223 further comprising means for
removing vapor from inside the pipe at at least one point along the
pipe.
234. The apparatus of claim 220 further comprising means for
removing vapor from the pipe at a least one bend and wherein the
pipe is serpentine and has at least one weir at an effective
distance from a bend.
235. The apparatus of claim 221 further comprising removing vapor
from the pipe at a least one bend and wherein the pipe is
serpentine and has at least one weir at an effective distance from
a bend.
236. The apparatus of claim 222 further comprising removing vapor
from the pipe at a least one bend and wherein the pipe is
serpentine and has at least one weir at an effective distance from
a bend.
237. The apparatus of claim 223 further comprising removing vapor
from the pipe at a least one bend and wherein the pipe is
serpentine and has at least one weir at an effective distance from
a bend.
238. The apparatus of claim 222 further comprising a tank for
holding solubilizing agent connected to the pipe at a point other
than the outlet.
239. The apparatus of claim 222 further comprising a recycle line
connecting the pipe at a point nearer to the outlet than the inlet
with the pipe at a point nearer the inlet than the outlet.
240. The apparatus of claim 228 further comprising a flow line from
the polycondensation reactor to the pipe at a point other than the
outlet.
Description
FIELD OF THE INVENTION
[0001] The invention relates to polyester processes using a pipe
reactor and to corresponding apparatuses. More particularly, the
invention relates to processes and to corresponding apparatuses
including an esterification pipe reactor operated in an upflow or
downflow mode, especially in a regime including stratified
flow.
BACKGROUND OF THE INVENTION
[0002] As the business of manufacturing polyesters becomes more
competitive, alternative processes have become highly desirable.
Relevant background for this invention is given in a U.S. patent
application related to the present one and filed the same day
entitled "Polyester Process Using a Pipe Reactor" with the
inventor, Bruce Roger DeBruin; this latter application is hereby
incorporated by reference to the extent that it does not contradict
the disclosures in the present application.
[0003] Another related U.S. patent application filed the same day
as the present one and entitled, "Polyester Process Using a Pipe
Reactor", with the inventors, Bruce Roger Debruin and Daniel Lee
Martin is also hereby incorporated by reference to the extent that
it does not contradict the disclosures in the present
application.
[0004] In addition, related cases U.S. application Ser. No.
10/013,318 filed Dec. 7, 2001 and U.S. Provisional Application
Serial No. 60/254,040 filed Dec. 7, 2000 are both incorporated by
reference to the extent that they do not contradict statements
herein.
SUMMARY OF THE INVENTION
[0005] It is an object of this invention to provide polyester
processes using a pipe reactor. Thus, this invention relates to a
process for making a pre-polyester comprising: providing an
esterification pipe reactor comprising a pipe, the pipe having an
inlet and an outlet and constructed such that flow inside the pipe
from the inlet to the outlet follows a path that is not totally
vertical nor totally horizontal; and reacting one or more reactants
flowing in the pipe towards the outlet under esterification
reaction conditions to form the pre-polyester.
[0006] The invention also relates to similar processes wherein the
pipe is constructed such that flow inside the pipe from the inlet
to the outlet follows an overall upward (outlet higher than inlet),
but not totally vertical path; this path may be in addition
generally non-downward, non-vertical.
[0007] Further, the invention relates to any of these processes
wherein stratified flow appears in the pipe.
[0008] Similarly, the invention relates to a process for making a
polyester oligomer, a polyester or both comprising: performing any
of the aforementioned processes for making a pre-polyester; and
reacting the pre-polyester and optionally other reactants, under
polycondensation reaction conditions, to form the polyester
oligomer, the polyester or both.
[0009] The invention also relates to processes corresponding to
those described here wherein the pipe is constructed such that flow
inside the pipe from the inlet to the outlet follows an overall
downward (outlet lower than inlet), but not totally vertical path;
this path may be in addition generally non-upward,
non-vertical.
[0010] A further object of this invention is to provide apparatuses
for polyester processes using a pipe reactor. Thus, this invention
relates to apparatuses corresponding to the processes described
above.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] The accompanying drawings, which are incorporated in and
constitute a part of this specification, illustrate several
embodiments of the invention and together with the description
serve to explain the principles of the invention.
[0012] FIG. 1 shows typical embodiments of the polyester processes
and apparatuses of the present invention.
KEY TO NUMBER DESIGNATIONS IN FIG. 1
[0013] 1 tank (optional)
[0014] 1A line from tank to pipe (optional)
[0015] 3 pipe inlet
[0016] 5 pipe of esterification pipe reactor
[0017] 7 vapor disengager (optional)
[0018] 7A vapor line (optional)
[0019] 9 recycle line (optional)
[0020] 11 pipe outlet
[0021] 15 polycondensation reactor (optional and shown as a pipe
reactor)
[0022] 15A line from polycondensation reactor to pipe
(optional)
DETAILED DESCRIPTION OF THE INVENTION
[0023] In this disclosure and the claims that follow, unless
otherwise indicated, the term polyester is used in a broad sense
and refers to a polymer containing more than 100 ester linkages (or
more than 100 corresponding linkages in the case of derivatives of
"straight" or "pure" polyesters such as polyetheresters, polyester
amides and polyetherester amides). Similarly, polyester monomers
would have 1 to 2 such linkages, polyester dimers 3 to 4 such
linkages, polyester trimers 5 to 6 such linkages and polyester
oligomers 7 to 100 such linkages. Pre-polyester refers to polyester
monomers, dimers, trimers, oligomers and combinations of these.
[0024] For simplicity, polyester processes will be understood to
include processes for making pre-polyesters when used in this
disclosure and the claims that follow, unless indicated
otherwise.
[0025] The processes according to the present invention include a
process for making a pre-polyester comprising providing an
esterification pipe reactor comprising a pipe, the pipe having an
inlet and an outlet and constructed such that flow inside the pipe
from the inlet to the outlet follows a path that is not totally
vertical nor totally horizontal; and reacting one or more reactants
flowing in the pipe towards the outlet under esterification
reaction conditions to form the pre-polyester.
[0026] More specifically, the pipe may be constructed such that
flow inside the pipe from the inlet to the outlet follows an
overall upward (outlet higher than inlet), but not totally vertical
path; this path may be in addition generally non-downward,
non-vertical. Further, the pipe may substantially empty; that is
substantially free of mechanical or structural internals (reactants
and the like not included of course). The pipe is understood to be
hollow in the context of this disclosure and the claims that
follow.
[0027] For simplicity, esterification is taken to include,
throughout this disclosure and the claims that follow, not only its
common meaning, but ester exchange as well.
[0028] The processes according to the present invention also
include processes for making a polyester oligomer, a polyester or
both comprising performing (the steps of) any of the processes for
making a pre-polyester previously described and reacting the
pre-polyester and optionally other reactants, under
polycondensation reaction conditions, to form the polyester
oligomer, the polyester or both. This last mentioned step of
reacting under polycondensation reaction conditions may be carried
out in a polycondensation pipe reactor or other type of reactor for
polycondensation.
[0029] The reactions taking place as part of the processes
according to the present invention ordinarily produce water (and
perhaps other types of) vapor, which unless removed, may
significantly reduce product yield. Thus, the processes of the
present invention may further comprise removing vapor from inside
the pipe.
[0030] Given space limitation normally present at manufacturing
sites, it may be convenient for the pipe to be serpentine; that is,
having at least one bend. One preferred orientation for the pipe in
accordance with this is shown in FIG. 1. The pipe 5 has several
horizontal zones joined by bends.
[0031] In the reaction systems covered by the processes of the
present invention, there may be solubility problems involving one
or more reactants. For example, terephthalic acid is not very
soluble in ethylene glycol, thus making it difficult to get the two
to react in making polyethylene terephthalate. Thus, the processes
of the present invention may further comprise adding a solubilizing
agent into the pipe. For purposes here, a solubilizing agent makes
one or more reactants more soluble in the other(s) or the reaction
mixture generally; in this context (in reference to solubilizing
agents), reactants will be taken as only those that are precursors
for polyester monomers (as solubilizing agents are not such
precursors). Suitable solubilizing agents include those comprising
a polyester monomer, dimer and/or trimer; those comprising a
polyester oligomer; those comprising a polyester; those comprising
organic solvents such as chlorinated aromatics (like
trichloro-benzene) and mixtures of phenol and chlorinated
hydrocarbons (like tetrachloroethane), tetrahydrofuran or dimethyl
sulfoxide; as well as those comprising combinations of these. Such
agents comprising a polyester oligomer, especially of the type
being produced in the process, are often preferred. These agents
may be mixed with reactants prior to addition to the pipe or added
to the pipe separately in whole or in part. If mixed with reactants
(here polyester monomer precursors) in any way, the solubilizing
agent would be considered to be the mixture less any such
reactants.
[0032] Many different types of reactants or mixtures of reactants
may be used in forming polyesters and pre-polyesters according to
the processes of the present invention, the types or mixtures of
reactants comprising a dicarboxylic acid (abbreviated here as a
diacid), a diol, a diester, a hydroxy ester, a carboxylic acid
ester (abbreviated here as an acid ester), a hydroxy carboxylic
acid (abbreviated here as a hydroxy acid) or combinations thereof.
It is possible that related materials such as tricarboxylic acids
and other such multifunctional materials could also be employed. It
should be understood that acid in this context would include
corresponding mono, di or higher order salts. Of course, the
pre-polyesters and polyesters being formed may be in turn reactants
themselves.
[0033] More specific reactants or mixtures of reactants of interest
comprise aromatic dicarboxylic acids preferably having 8 to 14
carbon atoms, aliphatic dicarboxylic acids preferably having 4 to
12 carbon atoms, or cycloaliphatic dicarboxylic acids preferably
having 8 to 12 carbon atoms. Such comprise terephthalic acid,
phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid,
cyclohexanedicarboxylic acid, cyclohexanediacetic acid,
diphenyl-4,4'-dicarboxylic acid, dipheny-3,4'-dicarboxylic acid,
2,2,-dimethyl-1,3-propandiol, dicarboxylic acid, succinic acid,
glutaric acid, adipic acid, azelaic acid, sebacic acid, mixtures
thereof, and the like. The acid component can be fulfilled by the
ester thereof, such as with dimethyl terephthalate.
[0034] Further more specific reactants or mixtures of reactants
comprise cycloaliphatic diols preferably having 6 to 20 carbon
atoms or aliphatic diols preferably having 3 to 20 carbon atoms.
Such comprise ethylene glycol (EG), diethylene glycol, triethylene
glycol, 1,4-cyclohexane-dimethanol, propane-1,3-diol,
butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol,
neopentylglycol, 3-methylpentanediol-(2,4),
2-methylpentanediol-(1,4), 2,2,4-trimethylpentane-diol-(1,3),
2-ethylhexanediol-(1,3), 2,2-diethylpropane-diol-(1,3),
hexanediol-(1,3), 1,4-di-(hydroxyethoxy)-b- enzene,
2,2-bis-(4-hydroxycyclohexyl)-propane, 2,4-dihydroxy-1,1,3,3-tetra-
methyl-cyclobutane, 2,2,4,4 tetramethylcyclobutanediol,
2,2-bis-(3-hydroxyethoxyphenyl)-propane,
2,2-bis-(4-hydroxypropoxyphenyl)- -propane, isosorbide,
hydroquinone, BDS-(2,2-(sulfonylbis)4,1-phenyleneoxy-
))bis(ethanol), mixtures thereof, and the like. Pre-polyesters and
polyesters may be prepared from one or more of the above type
diols.
[0035] Some preferred comonomers comprise terephthalic acid,
dimethyl terephthalate, isophthalic acid, dimethyl isophthalate,
dimethyl-2,6-naphthalenedicarboxylate, 2,6-naphthalenedicarboxylic
acid, ethylene glycol, diethylene glycol,
1,4-cyclohexane-dimethanol (CHDM), 1,4-butanediol,
polytetramethyleneglyocl, trans-DMCD
(trans-dimethyl-1,4-cyclohexane dicarboxylate), trimellitic
anhydride, dimethyl cyclohexane-1,4-dicarboxylate, dimethyl
decalin-2,6 dicarboxylate, decalin dimethanol, decahydronaphthalane
2,6-dicarboxylate, 2,6-dihydroxymethyl-decahydronaphthalene,
hydroquinone, hydroxybenzoic acid, mixtures thereof, and the like.
Bifunctional (A-B type where the ends are not the same) comonomers,
such as hydroxybenzoic acid may also be included.
[0036] Some specific reactants or mixtures of reactants of very
special interest comprise terephthalic acid (TPA; understood to
include crude, purified (PTA) or that in between), dimethyl
terephthalate (DMT), cyclohexane dimethanol (CHDM), isophthalic
acid (IPA), ethylene glycol (EG) or combinations thereof.
[0037] Many types of polyesters may be made using the processes of
the present invention. Two of special interest are polyethylene
terephthalate (PET) and PETG (PET modified with CHDM).
[0038] Ranges stated in this disclosure and the claims that follow
should be understood to disclose the entire range specifically and
not just end points(s). For example, disclosure of the range 0 to
10 should be taken to specifically disclose 2, 2.5, and 3.17 and
all other number subsumed in the range and not just 0 and 10.
Further a disclosure of C1 to C5 (one to five carbon) hydrocarbons
would be a specific disclosure of not only C1 and C5 hydrocarbons,
but also of C2, C3, and C4 hydrocarbons; ranges that are clearly
meant to be ranges of integers should be understood
correspondingly.
[0039] One area of intense interest regarding polyester processes
using a pipe reactor is the effect of flow regime in the pipe.
Surprisingly, it has been determined that under many circumstances
it may be desirable to operate the esterification pipe reactor, at
least in part, in a stratified flow regime. Accordingly, the
processes of the present invention include those previously
described wherein stratified flow appears in the pipe (of an
esterification pipe reactor). For this purpose, stratified flow may
be defined as a flow pattern in a pipe in which liquid flows along
the bottom and vapor flows over a liquid-vapor interface. Pipe
reactors can be designed by those of ordinary skill in the art to
meet this criteria in operation by application of standard
engineering design techniques with reference to the disclosures
herein. hI the systems considered here, operation so that
stratified flow appears in the pipe will produce two, three or more
phase systems.
[0040] Given different pipe designs, it may be desirable to operate
with stratified flow in a certain given percentage or section(s) of
the pipe. Calculations to determine needed parameters may be
performed by those of ordinary skill in the art using standard
engineering tools after consultation of the disclosures herein.
[0041] Esterification pipe reactors operated to produce liquid
superficial velocities inside the pipe of less than 0.15 m/s and
corresponding vapor superficial velocities less than 3.0 m/s, both
across any full cross sectional area inside the pipe perpendicular
to the (overall) flow path in the pipe (at that cross section) will
in very many of the systems considered herein be in a stratified
flow regime, at least in part. Even if not, the regime present
should be acceptable. Thus, the processes of the present invention
include those previously described wherein the liquid superficial
velocity is less than 0.15 m/s (with one preferred range of 0.01 to
0.15 m/s for the liquid) and the vapor superficial velocity is less
than 3.0 m/s (with one preferred range of 0.01 to 3.0 m/s and
another of 0.6 to 3.0 m/s for the vapor) across any full cross
sectional area inside the pipe perpendicular to the (overall) flow
path in the pipe (at that cross section). (Of course, each phase
must be moving at some point or there can be no stratified
flow).
[0042] Given different pipe designs, it may be desirable to operate
with superficial velocities as above in a certain given percentage
or section(s) of the pipe. Calculations to determine needed
parameters may be performed by those of ordinary skill in the art
using standard engineering tools after consultation of the
disclosures herein.
[0043] Two parameters of interest in the art relating to the
present invention are the Baker plot parameters, B.sub.x and
B.sub.y. These are defined as
B.sub.x=(G.sub.L.lambda..psi.)/G.sub.G, dimensionless and
B.sub.y=(G.sub.G/.lambda.), 1b/(sec ft.sup.2)
[0044] where, .lambda.=(.rho.'.sub.c.rho..sub.L').sup.1/2;
.psi.=(1/
.sigma.')(.mu..sup./.sub.L/(.rho.'.sub.L).sup.2)).sup.1/3;G.sub.G=vapor
mass velocity; G.sub.L=liquid mass velocity; .mu..sup./.sub.L=ratio
of liquid viscosity to water viscosity, dimensionless;
.rho.'.sub.c=ratio of vapor density to air density, dimensionless;
.rho.'.sub.L=ratio of liquid density to water density,
dimensionless; .sigma.'=ratio of liquid surface tension to water
surface tension, dimensionless; and air and water properties are at
20.degree. C. (68.degree. F.) and 101.3 kPa (14.7 lbf/in.sup.2).
See Perry's Chemical Engineers' Handbook, 6th ed., pp 5-40 and
5-41, hereby incorporated by reference for this purpose.
[0045] Esterification pipe reactors operated such that B.sub.x is
less than 4.0 while B.sub.y is less than 2.0 or B.sub.x is greater
than or equal to 4.0 while (log.sub.10 B.sub.y) is less than or
equal to -0.677(log.sub.10 B.sub.x)+0.700 on average across any
full cross sectional area inside the pipe perpendicular to the
(overall) flow path in the pipe (at that cross section) will in
very many of the systems considered herein be in a stratified flow
regime, at least in part. Even if not, the regime present should be
acceptable. Thus, the processes of the present invention include
those previously described wherein B.sub.x is less than 4.0 while
B.sub.y is less than 2.0 or B.sub.x is greater than or equal to 4.0
while (log.sub.10 B.sub.y) is less than or equal to
-0.677(log.sub.10 B.sub.x)+0.700 on average across any full cross
sectional area inside the pipe perpendicular to the (overall) flow
path in the pipe (at that cross section).
[0046] Given different pipe designs, it may be desirable to operate
with B, and By as above in a certain given percentage or section(s)
of the pipe. Calculations to determine needed parameters may be
performed by those of ordinary skill in the art using standard
engineering tools after consultation of the disclosures herein.
[0047] The processes according to the present invention also
include those corresponding to those described above wherein the
pipe is constructed such that flow inside the pipe from the inlet
to the outlet follows an overall downward (outlet lower than
inlet), but not totally vertical path and such path may be in
addition generally non-upward, non-vertical.
[0048] The apparatuses according to the present invention include
those corresponding to the processes of the present invention. In
particular, an apparatus for making a pre-polyester comprising: an
esterification pipe reactor comprising a pipe, the pipe having an
inlet and an outlet and constructed such that flow inside the pipe
from the inlet to the outlet follows a path that is not totally
vertical nor totally horizontal, and wherein pre-polyester forming
reactants are passed towards the outlet.
[0049] More specifically, the pipe may be constructed such that
flow inside the pipe from the inlet to the outlet follows an
overall upward, but not totally vertical path and this path may
also be generally non-downward, non-vertical. The pipe may also be
substantially empty (as defined previously).
[0050] The apparatuses according to the present invention also
include those for making a polyester oligomer, a polyester or both
comprising any of the apparatuses previously described and a
polycondensation reactor connected to the outlet of the pipe; this
last mentioned polycondensation pipe reactor may be a
polycondensation pipe reactor or of any other type suitable for
polycondensation.
[0051] In reference to the apparatuses of the present invention
connected means directly or indirectly (through a bridging piece(s)
of process equipment) in fluid communication.
[0052] As discussed previously, it is often important to remove
vapor from inside the pipe, so the apparatuses of the present
invention may further comprise means for removing vapor from inside
the pipe at at least one point along the pipe. This point along the
pipe could include the inlet or the outlet. In addition or instead
of removal from the pipe, vapor could be removed outside of the
pipe, generally and/or prior to polycondensation and/or during
polycondensation. Means for such vapor removal include vapor
disengagers, vents and other devices known in the art. See Perry's
Chemical Engineers' Handbook, 7th ed., pp 14-82 to 14-95, hereby
incorporated by reference for this purpose.
[0053] Also as discussed previously, the pipe may be
serpentine.
[0054] One variation on the apparatuses of the present invention
possible is the addition of a tank for holding solubilizing agent
(which may be mixed with reactants (polyester monomer precursors
here) if desired) that is connected to the pipe at a point other
than the outlet. Further, a recycle line connecting the pipe at a
point nearer to the outlet than the inlet with the pipe at a point
nearer the inlet than the outlet could be employed at least for
addition of recycle as a solubilizing agent to the pipe. Similarly,
a flow line from the polycondensation reactor to the pipe at a
point other than the outlet could also be added.
[0055] The apparatuses according to the present invention also
include those corresponding to those described above wherein the
pipe is constructed such that flow inside the pipe from the inlet
to the outlet follows an overall downward, but not totally vertical
path and such path may be in addition generally non-upward,
non-vertical.
[0056] One special consideration for this last mentioned class of
apparatuses according to the present invention is keeping the upper
sections of the pipe from running dry when the pipe is serpentine.
Thus, the apparatuses of the present invention include those
further comprising means for removing vapor from the pipe at a
least one bend and wherein the pipe is serpentine and has at least
one weir at an effective distance from a bend. Means for vapor
removal is as previously discussed. Effective distance for the weir
refers to a hydraulically effective distance to achieve the
objective of keeping the upper pipe sections from going totally
dry; this can be determined by those of ordinary skill in the art
using standard engineering methods following study of the
disclosures herein.
[0057] FIG. 1 illustrates the apparatuses of the present invention
as well as the corresponding processes. Optional tank 1 is for
storage of solubilizing agent which may be mixed with reactants. It
is connected (if present) by 1A to the pipe of the esterification
pipe reactor 5. Pipe inlet 3 is where fresh reactants are
ordinarily charged to the reactor and is a reference point for flow
through the pipe 5. Pipe 5 is shown in a preferred orientation such
that several horizontal sections are bridged by upward bends and
the inlet 3 is below the pipe outlet 11 in elevation. During
operation, reactants flow through the pipe 5 forming pre-polyester.
Shown here near the pipe outlet 11 is an optional vapor disengager
7 and vapor line 7A for discharge of vapor from the flow in the
pipe; as explained previously, vapor build up may negatively affect
product yield in the reactor system. Flow through the pipe 5 leaves
at the pipe outlet 11. Optionally, flow may be recycled through the
recycle line 9. Flow from the pipe outlet 11 optionally enters the
polycondensation reactor 15 (if present) which may be a
polycondensation pipe reactor as shown. Optionally, some flow from
the polycondnesation reactor 15 may be sent to the pipe 5 through
the line 15A. Flows through 9 and 15A may act as solubilizing
agents as discussed above.
EXAMPLES
[0058] The invention can be further illustrated by the following
examples, but it should be understood that these examples are
included merely for purposes of illustration and are not intended
to limit the scope of the invention unless otherwise specifically
indicated. Any titles in the examples are given for convenience and
should not be taken as limiting.
Example 1
[0059] Using ASPEN modeling, exemplary volumes and pipe diameters
were calculated for a commercial scale pipe reactor system for
esterification of purified terephthalic acid (PTA) in ethylene
glycol (EG). ASPEN Plus version 11.1 with Polymers Plus and ASPEN's
PET Technology was used. The esterification reactor is modeled as a
series of 5 CSTR reactor models followed by a plug flow reactor
model. The results of the modeling and a pipe sizing for a
stratified flow pipe reactor for esterification using polyester
monomer recirculated from the exit to the entrance as a
solubilizing agent for the feed PTA and taking off water vapor only
at the end of the reactor length are shown in Table 1.
1TABLE 1 Calculations for esterification in a single recirculating
pipe reactor with vapor takeoff Example: only at the end of the
reactor PTA feed rate (lb/hr): 31320 Recirculation ratio (lbs of
recirc/lb of 4.0 product): feed mole ratio (mole EG/mole PTA): 1.6
% conversion of acid end groups: 96% Temperature (.degree. C.): 285
maximum pressure (psig): 52.1 recirculating reactor liquid volume
(cu. ft): 2648 number of parallel pipes in reactor: 16
recirculating reactor pipe diameter (in): 16 recirculating reactor
maximum liquid 0.03 superficial velocity (ft/s): recirculating
reactor maximum vapor 9.8 superficial velocity (ft/s):
Example 2
[0060] Using ASPEN modeling, exemplary volumes and pipe diameters
were calculated for a commercial scale pipe reactor system for
esterification of purified terephthalic acid (PTA) in ethylene
glycol (EG). ASPEN Plus version 11.1 with Polymers Plus and ASPEN's
PET Technology was used. The esterification reactor is modeled as a
series of 5 CSTR reactor models followed by a plug flow reactor
model. The results of the modeling and a pipe sizing for a
stratified flow pipe reactor for esterification using polyester
monomer recirculated from the exit to the entrance as a
solubilizing agent for the feed PTA are shown in Table 2. This
example shows the efficiency effects of a single vapor takeoff
added in the middle of the reactor length.
2TABLE 2 Calculations for esterification in a single recirculating
pipe reactor with vapor takeoff in the middle of the reactor and
Example: at the end of the reactor PTA feed rate (lb/hr): 31320
Recirculation ratio (lbs of recirc/lb of 4.0 product): feed mole
ratio (mole EG/mole PTA): 1.6 % conversion of acid end groups: 96%
Temperature (.degree. C.): 285 maximum pressure (psig): 52.1
recirculating reactor liquid volume (cu. ft): 1236 number of
parallel pipes in reactor: 12 recirculating reactor diameter (in):
16 recirculating reactor maximum liquid 0.05 superficial velocity
(ft/s): recirculating reactor maximum vapor 10.8 superficial
velocity (ft/s):
Example 3
[0061] Using ASPEN modeling, exemplary volumes and pipe diameters
were calculated for a commercial scale pipe reactor system for
esterification of purified terephthalic acid (PTA) in ethylene
glycol (EG). ASPEN Plus version 11.1 with Polymers Plus and ASPEN's
PET Technology was used. The esterification reactor is modeled as a
series of 5 CSTR reactor models followed by a plug flow reactor
model. The results of the modeling and a pipe sizing for a series
of stratified flow pipe reactors for esterification using polyester
monomer recirculated from the exit of the first pipe reactor to the
entrance of the first pipe reactor as a solubilizing agent for the
feed PTA are shown in Table 3. This example shows the optimization
effects of using recirculation only as required for solubility
concerns and using plug reaction profile with no recirculation as
much as possible.
3TABLE 3 Calculations for single recirculating pipe reactor with
two vapor takeoffs followed by plug flow pipe Example: optimized
for total volume PTA feed rate (lb/hr): 31320 Recirculation ratio
(lbs of recirc/lb 4.0 of product): feed mole ratio (mole EG/mole
PTA): 1.6 % conversion of acid end groups: 96% Temperature
(.degree. C.): 285 maximum pressure (psig): 52.1 recirculating
reactor liquid volume (cu. ft): 318 plug flow reactor liquid volume
(cu. ft): 353 number of parallel pipes in recirculating 8 reactor:
recirculating reactor diameter (in): 16 recirculating reactor
maximum liquid 0.07 superficial velocity (ft/s): recirculating
reactor maximum vapor 5.5 superficial velocity (ft/s): number of
parallel pipes in plug flow reactor: 6 plug flow reactor diameter
(in): 12 plug flow reactor maximum liquid 0.03 superficial velocity
(ft/s): plug flow reactor maximum vapor 1.8 superficial velocity
(ft/s):
Example 4
[0062] Lab-Model Comparison
[0063] Lab Scale Reactor
[0064] A lab scale esterification pipe reactor was built to
demonstrate such esterification of PTA and EG in a laboratory
setting. The lab unit consisted of a pipe reactor made of 664.75
inches of 0.5"18 BWG stainless tubing heated by electric tracing, a
1200 ml receiver with agitator for receiving the output of the pipe
reactor and acting as a disengagement zone to allow the removal of
vapors, a recirculating monomer gear pump which pumps liquid
oligomer from the receiver back into the inlet of the pipe reactor,
and a PTA/EG paste feed system which feed raw materials into the
recirculating loop.
[0065] The reactor was started by charging a PTA based CHDM
modified (2.5 weight percent) oligomer of approximately 96%
conversion into the receiver (C-01) and filling the pipe reactor
with this oligomer in recirculating mode. After recirculating the
oligomer at temperature, a PTA/EG paste feed was introduced into
the recirculating flow. After the reactor reached steady state,
samples were taken from the C-01 receiver at a rate equal to the
product generation rate .
[0066] These samples were analyzed for percent conversion by proton
NMR analysis to determine the extent of reaction that took place in
the pipe reactor. Percent Conversion based on Esters were
determined by Proton NMR using a Trifluoroacetic Anhydride
Method.
[0067] Ten mg of the sample to be analyzed is dissolved in 1 ml of
a solvent mixture of chloroform-d with 0.05% Tetramethylsilane
(TMS)/trifluoroacetic acid-d/trifluoroacetic anhydride in a 72/22/8
volume ratio. The mixture is heated to 50.degree. C. and stirred as
needed to completely dissolve the sample to be analyzed.
[0068] The appropriate amount of the sample solution is transferred
into a 5 mm NMR tube and the tube is capped. The proton NMR signal
is recorded using an average of 64 signals collections. The NMR
signal using a 600 MHz NMR and a NMR pulse sequence is collccted
which gives quantitative proton NMR signals and also decouples the
carbon 13 NMR frequencies. The NMR spectrum is analyzed by
measuring the correct areas calculating the percent conversion of
acid groups to ester groups by the areas and calculations
below:
[0069] Areas between the following chemical shift points referenced
to TMS are measured, and percent conversion calculated using the
formula.
[0070] Area A=7.92 ppm to 8.47 ppm
[0071] Area B=5.01 ppm to a valley between 4.82 and 4.77 ppm
[0072] Area C=4.82 ppm to a valley between 4.74 and 4.69 ppm
[0073] Area D=A valley between 4.28 ppm and 4.18 ppm to a valley
between 4. 10 and 4.16 ppm
[0074] Area E=A valley between 4. 10 ppm and 4.16 ppm to a valley
between 4.0 and 4.08 ppm
[0075] Area F=8.6 ppm to 8.9 ppm
[0076] Area G=7.55 ppm to7.8 ppm
[0077] Percent Conversion=100*(B+(0.5*C)+D+(0.5*E))/(A+F+G)
[0078] The samples were also analyzed by gas chromatograph for
percent DEG by mass to determine the rate of the side reaction. The
effect of residence time and recirculation ratio was seen by
varying the feed rate of the paste. Results from laboratory runs
can be seen in Table 4 below.
4TABLE 2 Recirc Paste Feed Feed Temp Pressure Rate Rate Mole Ratio
Measured Measured Experiment (.degree. C.) (psig) (lbs./hr)
(lbs./hr) (EG/PTA) % Conversion weight % DEG 1 285 0 67 1 1.8 94.2%
1.1% 2 285 0 67 1 1.8 93.7% 1.1% 3 285 0 67 1 1.8 92.5% 1.4% 4 285
0 67 1.5 1.8 92.7% 1.0% 5 285 0 67 2 1.8 90.9% 0.6% 6 285 0 67 2.5
1.8 87.2% 0.7% 7 285 0 67 3 1.8 64.2% 0.2% 8 285 0 67 3.5 1.8 67.1%
0.6% 9 285 0 67 4 1.8 51.9% 0.3% 10 285 0 67 3.5 1.8 77.4% 0.3%
[0079] Model Comparison
[0080] An ASPEN model was used to simulate the lab apparatus
previously described in this example. In this case, ASPEN 11.1 with
Polymers Plus, and ASPEN's PET Technology was used for the modeling
with a model configuration similar to the one described for
examples 1-3. Neither model configuration nor software were
significantly different from that used in examples 1-3. In order to
correctly simulate the dissolution of PTA into the oligomer at
different conditions in the lab, it was sometimes necessary to add
dissolution kinetics to the model. Table 5 shows three comparisons
of lab runs with the model without dissolution kinetics included;
this model was found to be of reasonable accuracy when the
experimental conditions resulted in completely dissolved PTA as in
these runs. Table 5 also shows two examples of comparisons of lab
runs with the model including the dissolution kinetics; this model
including the dissolution kinetics closely matches the measured
conversion when free PTA is present at the end of the lab scale
pipe reactor as in these runs. Conversion is defined in this
context as the percentage of reactive (acid if use PTA as here) end
groups in the liquid phase that are esterified as measured at the
outlet of reactor.
5TABLE 5 Paste Monomer Mole Model Paste Circu- Ratio Unreacted
Predicted Measured feed lation Temp. (EG/ PTA % Con- % Con- (g/min)
(g/min) .degree. C. PTA) Weight % version version Completely
Dissolved PTA - No Dissolution Kinetics in Model 8 507 263.2 1.8
0.00 97.053 95.170 8 507 253.9 1.8 0.00 96.645 93.750 15 507 265.5
1.8 0.00 96.269 91.630 PTA Not Completely Dissolved/Dissolution in
Kinetics Model 19 507 261.5 1.8 2.93 90.935 86.500 15 507 261.5 1.8
3.34 90.228 85.490
[0081] The specific embodiments described and shown in the
specification and drawings should be taken as illustrative of the
present invention and not for purposes of limiting the claims that
follow, unless specifically indicated otherwise.
* * * * *